Ester-linked acyl amides and method of making same



Patented Aug. 7, 1945 N TEDQ ESTER-LINKED ACYL AMIDES AND METHOD OF MAKING SAME Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, M0., assignors to Petrolite Corporation, Ltd., Wilmington, Del, a

corporation of Delaware No Drawing. Original application June 15, 1942,-

Serial No. 447,156. Divided and this application August 2, 1943, Serial No. 497,123

10 Claims.

This invention relates to a new chemical prodnot or composition of matter, our present application being a division of our co-pending application Serial No; 447,156, filedJune 15, 1942, which subsequently matured as U. S. Patent No. 2,353,699, dated July 18, 19414. V

The main object of our invention is to provide a new chemical product or compound that is particularly adapted for use as a demulsifier in the resolution of crude oil emulsions.

Another object of our invention is to provide a practicable method for manufacturing said new chemical product or compound. 1

Although one of the primary objects of our invention is to provide a new compound or composition of matter that is an efficient demulsifier for crude oil emulsions of the water-in-oil type, the said compound or composition of matter is adapted for use in other arts, as hereinafter indicated.

We have discovered that if one oxyalkylates glycerol so as to introduce at least three oxyalkylene radicals for each hydroxyl group, and if the product so obtained is reacted with a polybasic carboxy acid having not over eight carbon atoms, and in such a manner as to yield a fractional ester, due to the presence ofat least onefree carboxyl radical, one can then esterify said acidic material or intermediate product with at least one mole of 'an alcoholic compound of the type herein described to give a variety of new compositions of matter which have utility in various arts, and particularly in the demulsification of crude oil. The compounds herein contemplated may b produced in any suitable manner, but are usually manufactured by following one of two general procedures. In one of said procedures the oxyalkylated glycerol, which is, in essence, a polyhydric alcohol, is reacted with a polybasic acid so as to give an acidic material or intermediate product, which, in turn, is reacted with an'alcoholic body of the kind hereinafter described, and momentarily indicated by the formula R1(OH) m. Generically,-the alcoholic body herein contemplated may be considered a member of the class in which m may vary from 1 to 10, although the specific significance of m in the present instance will be hereinafter indicated. The second procedure is to react an alcohol of the formula type R1(Ol1)m with a polybasic acid so as to produce an intermediate product, and then react said intermediate product or fractional ester with the selected oxyalkylated glycerol.

Glycerol may be conveniently indicated by the following formula:

If treated with an oxyalkylating agent, and momentarily consideration will be limited to an oxyethylating agent, one may obtain an oxyethylated glycerol of the following formula type:

(cznlown in which the value of n may vary from 3 to 10 and all the values of n need not be identical.

If a polybasic carboxy acid be indicated by the formula:

in which n" has the value of one ortwo. Similarly, if two moles of the polybasic acid be used, then the compound may be indicated bythe following formula: 1

(oznlonooomooomn c3H503(o2H1o ..'oocmooonn" (C2H40)n'H Likewise, if three moles of a polybasic acid are employed, the compound may be indicated by the following formula:

If a fractional ester of the kind exemplified by the three preceding formulae is reacted with one or more moles of an alcohol of the kind previously described in a generic sense as R1(OI-I) m, then obviously, one may obtain a material of the type indicated by the following formula:

[(CzH-iCUn'OOCR(COOH),W];

C3H5O3[(C2H4O) MEL:

in which as is 0, 1, or 2, y is 0, 1, 0r 2, and z is 1, 2, or 3, and :II' is 0 or 1, and y is 1 or 2.

by oxyalkylating agents, Without being limited to ethylene oxide. Suitable oxyalkylating agents include ethylene oxide, propylene oxide, butylene oxide and glycid, which, although not included, strictly speaking, by the unitary structure CnHZnO, is included within the meaning of the hereto appended claims and may be simply considered as a variant of propylene oxide, i. e., hydroxypropylene oxide. Similarly, where a carboxylic hydrogen atom appears, it may be replaced by metal, an ammonium radical or substituted ammonium radical, or by an organic group derived from an alcohol, such as an aliphatic alcohol, an aralkyl alcohol, or an alicyclic alcohol. It may also be converted into an amide, including a polyaminoamide. Thus, the preceding formula may be rewritten in its broader scope, as follows:

is intended to include any hydroxyl groups that remain.

If the compounds herein contemplated are obtainedunder usual conditions, at the lowest temperatures, then the monomeric form is most likely to result.

The production of the compounds herein contemplated is the result of one or more esterification steps. As is well known, esterification procedures can be carried out in various manners, but generally speaking, esterifications can be carried out at the lowest feasible temperatures by using one of several procedures. One procedure is to pass an inert dried gas through the mass to be esterified, and have present at the same time a small amount of a catalyst, such as dried I-ICl gas, a dried sulfonic acid, or the like. Another and better procedure, in many instances, is to employ the vapors of a suitable liquid, so as to remove any water formed and condense both the vapors of the liquid employed and the water in such a manner as to trap out the water and return the liquid to the reacting vessel. This procedure is commonly employed in the arts, and for convenience, reference is made to U. S. Patent No. 2,264,759, dated December 2, 1941, to Paul C. Jones.

Referring again to the last two formulae indicating the compounds under consideration, it can be readily understood that such compounds, in numerous instances, have the property of polyfunctionality. In View of this fact, where there is atleast one residual carboxyl and at least one residual hydroxyl, one would expect that under suitable conditions, instead of obtaining the monomeric compounds indicated, one would in reality obtain a polymer in the sense, for example, that polyethylene glycols represent a polymer of ethylene glycol. The term polymer is frequently used to indicate the polymerized product derived from a monomer in which the polymer has the same identical composition as the monomer. In the present instance, however, polymerization involves the splitting and loss of water so that the process is essentially self-esterification. Thus, strictly speaking, the polymeric compounds are not absolutely polymers of the monomeric compounds, but since, for all practical purposes, they can be so indicated, and since such practice is common in the arts concerned with materials of this type, it is so adopted here. Thus, reference in the appended claims to polymers is intended to include the self-esterification products of the monomeric compounds.

In view of what has been said, and in view of the recognized hydrophile properties of the recurring oxyalkylene linkages, particularly the oxyethylene linkage, it is apparent that the materials herein contemplated may vary from compounds which are clearly water-soluble through self-emulsifying oils, to materials which are bal- Sam-like and sub-resinous or semi-resinous in nature. The compounds may vary from monomers to polymers, in which the unitary structure appears a number of times, for instance, 10 or 12 times. It is to be noted that true resins, i. e., truly insoluble materials of a hard plastic nature, are not herein included. In other words, the polymerized compounds are soluble to a fairly definite extent, for instance, at least 5% in some solvents, such as water, alcohol, benzene, dichloroethyl ether, acetone, cresylic acid, acetic acid, ethyl acetate, dioxane, or the like. This is simply another way of stating that the polymerized product contemplated must be of the subresinous type, which is commonly referred to as an A resin, or a B resin, as distinguished from a C resin, which is a highly infusible, insoluble resin (see Ellis, Chemistry of Synthetic Resins (1935), pages 862, et seq.)

Reviewing the form as presented, it is obvious that one may obtain compounds within the scope disclosed, which contain neither a free hydroxyl nor a free carboxyl group, and one may also obtain a compound of the type in which there is present at least one free carboxyl or at least, one free hydroxyl, or both. The word polar has sometimes been used in the arts in this particular sense to indicate the presence of at least one free hydroxyl group, or at least, one free carboxyl group, or both. In the case of the free carboxyl group, the carboxylic hydrogen atom may, of course, be replaced by any ionizable hydrogen atom equivalent, such, for example, as a metal, an ammonium radical, a substituted ammonium radical, etc. In the hereto appended claims the word polar is used in this specific sense.

We are aware that compounds similar to those contemplated in the present instance may be derived from polyhydroxylated compounds having more than three hydroxyl groups. For instance, they may be derived from acyclic diglycerol, triglycerol, tetraglycerol, mixed poly.- glycerols, mannitol, sorbitol, various hexitols, dulcitol, pentaerythritol, sorbitan, mannitan, dipentaerythritol monoether, and other similar compounds. Such particular types in which higher hydroxylated materials are subjected to oxyalkylation and then employed in the same manner as oxyalkylated glycerol, is employed in the present instance, are not contemplated in this specific case, although attention is directed to the same.

Reference is also made to other oxyalkylated compounds which may be used as reactancts to replace oxyalkylated glycerol, or oxyalkylated ethylene glycol, which latter reactant is described in an application hereinafter referred to, to wit, our application Serial No. 384,598, filed March 21, 1941, now U. S. Patent No. 2,295,600, dated September 8, 1942. The reactants thus contemplated include the type in which there is an amino sixrcarbomatoms or less. the higherthe temperature employed, the easier it is to-obtain large yields of esterified product,

point ofwater. .ablexto use an acid which'is more resistant to or: amidornitrogen z atom. Particularly, when present in alow. molal type of. compoundp'rior to oxyalkylation, reference being made to polyhydroxylated materials," including thosehaving two or three hydroxyl groups, as well asthose haying morethanthree hydroxyl groups. For instance, the .oxyalkylated derivatives, particularly .the oxyethylated derivatives of ethyldiethanolamine, bis(hydroxyethyl) acetamide, the acetamide of tris(hydroxymethyl) aminomethane, tetrahydroxylated ethylene diamine, etc. Compounds may also be derived'from cyclic diglycerol and :the

like.

."Furthermore, for convenience, attentionis' directed' to assomewhat similar class of materials which are described in our application Seri'alNo. 384,598,? filed March'21, 19.41, now Patent No. 2,295,600, dated September 8, 1942.. .Said patent involves the use of the same type of alcoholic bodies-for reactants, but islimited, among other things,'; to': the compounds which. are essentially symmetrical in nature, for instance, involving the introduction of two alcoholic residues, whereas, inlthewpresent instance, one, two, or three, or more, might be. introduced.

As indicated previously, the polybasic acids employed are limitedtothe type having not more than-eight carbon atoms, for" example, oxalic, mal'onic, succinic, glutaric, adipic, maleic, and phthalic. Similarly, one may employ acids, such as'fumaric,.glutaconic,iand various others, such as citric, malic, tartaric, and the like. The selection of the particular tribasic or dibasic acid employed, is usually concerned largely with the convenience of-manufacture of the finished ester, 21111113150 theprice. of'the reactants. Generally speakinggphthalici acid or anhydride tends to produce resinous materials, and greater care mustbe employed if the ultimate or finalproduct benof a sub-resinous type. Specifically, the preferred type of polybasic acid is such as to contain Generally speaking,

although polymerization. may be stimulated.

Oxalic acid may becomparatively cheap, but it decomposes readily at slightly above the boiling For this reason it is more desirpyrol ysis. Similarly, when a, polybasic acid is available in:the form of an anhydride, such anhydride is apt to produce the ester with greater ease than'the acid itself. For this reason, maleic anhydride is particularly adaptable, and also everythingrelseconsidered, the cost is cmpara-, tively low-on a per molar basis, even though somewhat higher on a per pound basis. Succinic acid orthe anhydride has many attractive qualities of maleic anhydride, and thisis also true of adipic acid. For purposes'of brevity, the bulk of the examples, hereinafter illustrated, will refer to the use of maleic anhydride, although it is understood that any other suitable polybasic acid may be employed. Furthermore, reference is made to derivatives obtained by oxyethylation,

although, as previously pointed out, other oxyalkylating agents may be employed.

As far as the range of oxyethylated glycerols employed as reactants is concerned, it is our preference to employ those in which approxi-' mately to 24 oxyethylene groups have been introduced into a; single glycerol molecule. This means that approximately five to eight oxyethylene radicals have been introduced for each original hydroxyl group.

-7 ;,preceding-examples, except that oxyethylated z The oxyalkylation of'glycerol is a 'well. known procedure (-see Example 11 of German'PatentNo. 605,973, dated November 22, 1934, to I. G. Farbenindustrie, A. 'G.). The procedure indicated in the following three examples is substantially identical with that outlined in said aforementioned German patent.

GXYETHYLATED GLYcERoL Example 1 184 .v poundsof. glycerol are mixed with /2'%, by weight, of. caustic soda solution having a specific gravity of 1.383. .The caustic sodaacts as a catalyst. .The ethylene oxide is added in relatively small amounts,.for.instance, about 44 pounds at a time. The temperature employed is from -180" C. Generally speaking, .the gauge, pressure. during. the operation approximates 200 pounds at the maximum, and. when reaction is completed, drops to. zero, due to completeabsorption of the ethylene oxide. .When all the ethylene oxide has been absorbed and the reactants cooled, a second small.portion,.for instance,- 44 .more pounds of ethylene oxide, are added and the procedure repeated until the desired ratio. of. 15 pound'moles of ethylene oxide to. one pound mole of glycerol is obtained. This represents 660 pounds of ethylene oxide for 92 pounds of, glycerol.

'OXYETHYLATE'D 'LGLYCEROL Example 2 The ratio .of ethylene oxide is increased to .18 pound. moles for each-pound mole. of glycerol. Otherwise, thesame procedure is followed vasin Example 1, preceding.

'OXYETHYLATED GLYCEROL 1 Example 3 I The same procedure is followed as inthe two previous examples, except that the ratio of One'pound' mole of oxyethylated glycerol (1 to 15 ratio) prepared in the manner previously described is treated with one pound mole of maleic anhydride and heated at approximately thirty minutes to two hours, with constant stirring; so as to yield a monomaleate.

. OXYETHYLATED GLYcERonMALEATE Example 2 OXYETHYLATED GL-YCEROL MALEATE Ezrample 3 The same procedure'is followed as in the two prec'eding examples, except that three moles of --maleicanhydride are employed so as to obtain the trimaleate.

. OXYETHYIJATED GLYCEROL MALEATE Example 4 .;"I 'hewsame procedure is employed as in the amines, hydroxypropyl alkylamines, etc.

glycerol (ratio 1 to 18) 'is substituted in place of oxyethylated glycerol (ratio 1 to 15).

OXYETHYLATED GLYCEROL MALEATE Example 5 The same procedure is employed as in the preceding examples, except that oxyethylated glycerol (ratio 1 to 21) is'employed instead of oxyethylated glycerol (ratio 1 to or (1 to 18).

Previous reference has been made to an alcoholic body which has been defined generically by type formula R1(OH)m. The sub-generic class of alcoholic compounds employed as reactants in the manufacture of the present compounds, are materials commonly referred to as substituted amides characterized by the presence of a hydroxy hydrocarbon radical containing at least one alcoholic hydroxyl radical as a substituent for an amino hydrogen atom. Such hy-. droxylated amides are of the kind in which the acyl radical is derived from a detergent-forming acid.

' Detergent-forming acids are monocarboxy acids having more than 8 and not over 32 carbon atoms, and characterized by the fact that they combine with alkalies such as caustic soda. caustic potash, ammonia, triethanolamine, and the like, to produce soap or soap-like materials.

The best examples are, of course, the higher fatty acids, such as oleic acid, stearic acid, palmitic acid, etc. In addition to the higher fatty acids, other well known members of this class include resinic acids, abietic acids, naphthenic acids, and acids obtained by the oxidation of petroleum hydrocarbons and commonly referred to as oxidized Wax acids.

Generally speaking, the higher fatty acids are apt to contain from 12-14 carbon atoms as a lower limit, to 18-22 carbon atoms as an upper limit. Oxidized wax acids may contain as many as 32 carbon atoms.

It is well known, of course, that amides may be obtained by reaction between long chain carboxy acids and monoalkylolamines, such as mono- 1 ethanolamine, monopropanolamine, monobutanolamine, etc. The manufacture of such chemical compounds, particularly where derived from higher fatty acids, is described in British Patent No. 450,672, dated July 17, 1936, to Orelup. Another procedure which has been employed for the same purpose is to react the monoalkylolamine with the acyl chloride derived from a suitablecarboxy acid. Still another method employs the use of an alkylene oxide, such as ethylene oxide,

propylene oxide, butylene oxide, and the like, in connection with an amide. Reference is made to U. S. Patent No. 2,002,613, dated May 28, 1935, to Orthner and Keppler. This latter method for producing oxyamides is not limited to the use of alkylolamines, such as monoalkylolamines, dialkylolamines, or the like, as the raw material, but may emplo alkylolamines, arylamines, aralkylamines, alicyciic amines, etc., so as to obtain hydroxylated derivatives. Naturally, the methods employing monoalkylamines, and particularly the process in which acyl chlorides are employed, may also use such materials as diethanolamine, dipropanolamine, dibutanolamine, and the like, Amides so obtained may have as many as six hydroxyl radicals in the aminohydrogen position.

It is known, of course, that when primary and secondary amines are reacted with various alkylene oxides, one may obtain hydroxyethyl alkyl- The reaction, for example, between a primary amine and ethylene oxide, yields a, material of the formula type HO.CH2.CH2.NHR. Such amines may be reacted with detergent-forming carboxy acids to give suitable amides.

Briefly, then, in a practical way amides can be derived from detergent-forming acids or some derivative, usually an ester. Indeed, esters are often more suitable reactants for amidification than the acids themselves. As to the manufacture of esters, see the following United States patents, to Wit: No. 1,160,595, dated Nov. 16, 1915, to Gruter et al.; No. 2,221,674, dated Nov. 12, 1940, to Ellis; and No. 2,177,407, dated Oct. 24, 1939, to Hansley. See also Organic Syntheses, volume X, page 88, 1930.

As to the procedure for the manufacture of acids or substituted amides, see the following United States patents: No.2.058,013, dated Oct. 20, 1936, to Henke et al.; No. 2,013,108, dated Sept. 3, 1935, to Reppe et al.; No. 1,475,477, dated Nov. 27, 1923, to Ellis; and No. 1,954,433, dated Apr. 10, 1934, to Thomas et al.

In any event, suitable amides having been obtained, either from the acids, esters, or any other derivatives, they may then be treated with ethylene oxide, propylene oxide, butylene oxide, glycid, or the like. Similarly, instead of obtaining the amides, one may obtain the substituted amides, i. e., the derivatives of amylamine, cyclohexylamine, aniline, benzylamine, or the like, particularly the substituted amides, in which the hydrocarbon radical replacing an amino hydrogen atom contains not over 7 carbon atoms. Such substituted amides then can be treated with oxyalkylating agents in the same manner previously described in connection with the amides.

Another suitable procedure is simply to react the selected ester or acid or other suitable derivative, with a hydroxylated primary amine, such as monoethanolamine, 'monopropanolamine, monobutanolamine, monoglycerylamine, tris(hydroxymethyl)aminomethane, and the like. Such reactants readily yield the hydroxylated amide of the kind contemplated.

Reactions can also be conducted with secondary hydroxylated amines of the kind exemplified by diethanolamine, dipropanolamine, diglyecrylamine, etc. When this latter type of reactants is employed, one is more apt to obtain a significant amount of esterified compound along with the amide derivative. The same also I applied when material of the type exemplified by ethyl ethanolamine, phenyl ethanolamine, cyclohexyl ethanolamine, etc., are employed for amidifica- RCON RC-ON where D is a hydro carbonradical.

CaHs .RC ON OH RCON OH CHzOH Our preferred amides are derivatives of fatty acids, and especially unsaturated fatty acids, such as oleic acid, ricinoleic acid, etc.

CoMPLETTD- MONOMERIC DERIVATIVE Example 1 One pound mole of a product of the kind describedunder the heading Oxyethylated glycerol maleate, Example 1 is. reacted with one pound mole of hydroxyethyl oleoamide, preferably in theabsence of any high boiling hydrocarbon. or inert solvent. However, if an inert vaporizing solvent is employed, it is generally necessary to use one which has a higher boiling range than xylene, and sometimes removal of such solvent might present a difficulty. In other instances, however, such high-boiling inert vaporizing sol- Vent, if employed, might be permitted to remain in the reacted mass and appear as a constituent or ingredient of the final product. In any event, ourpreference is to conduct the reaction in the absence of any such solvent and permit the reaction to proceed with the elimination of water. The temperature of reaction is about 186 to 260 C. and time of reaction about 20 hours.

. COMPLETED MONOMERIC DERIVATIVE Example 2 The same procedure is followed as in Completed monomeric derivative, Example 1, preceding. except that the dimaleate described under the heading-Oxyethylated glycerol maleate, Example 2 is used'instead ofthe monomaleate.

= Cor/Trims 'MONOMERIC DERIVATIVE Example 3 The same procedure is followed as in the two preceding examples, except that the trimaleate is substituted for the monomaleate or dimaleate in the two preceding examples.

COMPLETED MONOMERIC DERIVATIVE Example 4 COMPLETED MONOMERIC DERIVATIVE Ewample 5 The. same procedureis followed as in Example 3,1preceding, except that for each pound mole of trimaleatadnsteadof adding one pound mole of moles of hydroxyethyl oleoamide, for reaction.

COMPLETED MoNoMsR-ic .DERIVATIVE Example 6 Reference to the preceding examples will show that in eachand every instance oxyethylated glycerol (ratio 1 to 15) has beenemployed-as a raw material or primary reactant. In thepresent instance, a more highly oxyethylated glycerol is employed, to wit, one involving the ratio of 1 to 18. (See Oxyethylated glycerol maleate'Example 4,preceding.)

COMPLETED MoNoMEaIc DERIVATIVE Example 7 The same procedure is followed as in Example 6, immediately preceding, except that'the oxyethylated glycerol employed represents onehaving an even higher degree of oxyethylation. For xample, one indicated by the ratio of 1m 21. (See Oxyethylated glycerol maleate, Example 5, preceding.)

COMPLETED lVIONOll/IERIC DERIVATIVE Example 8 The same procedure isfollowed as in Examples 1 to 7, preceding, except that bis(hydroxyethyl) oleoamide is substituted for hydroxyethyl oleoamide. 4

COMPLETED MONOMERIC DERIVATIVE- Example 9 The same procedure is followed, as in Examples 1 to '7, preceding, except thathydroxyethyl 'ricinoleoamide is substituted for hydroxyethyl oleoamide.

COMPLETED MONOMERIC DERIVATIVE Example 10 'esterification catalyst, such as sulfuric acid, benzene sulfonic acid, or the like. This is the same general procedure as employed in the manufacture of ethylene glycol dihydrogen diphthalate. (See U. S. Patent No. 2,075,107, dated March 30, 1937, to Frasier.) Sometimes esterification is conducted most readily in the presence of an inert solvent, that carries away the water of esterification which may be formed, although as is readily appreciated, such water of esterification is absent when such type of reaction involves an acid anhydride, such as maleic anhydride, and a glycol. However, if water is formed, for instance, when citric acid is employed, then a solvent such as xylene may be present and employed to carry off the water formed. The mixture of xylene vapors and water vapors can be condensed so that the water is separated. The xylene is then returned to the reaction vessel for further circulation. This is a hydroxyethyl oleoamide, one adds three pound:

conventional and well known procedure and requires no further elaboration.

In the previous monomeric examples there is a definite tendency, in spite of precautions, at least in a number of instances, to obtain olymeric materials and certain cogeneric by-products. This is typical, of course, of organic reactions of this kind, and as is well known, organic reactions per se are characterized by the fact that 100% yields are the exception, rather than the rule, and that significant yields are satisfactory, especially in those instances where the by-products or cogeners may satisfactorily serve with the same purpose as the principal or intentional product. This is true in the present instance. In many cases when the compound is manufactured for purposes of demulsification, one is better off to obtain a polymer in the sense previously described, particularly a polymer Whose molecular weight is a rather small multiple of the molecular weight of the monomer, for instance, a polymer whose molecular weight is two, three, four, five, or six times the molecular Weight of the monomer. Polymerization is hastened by the presence of an alkali, and thus, in instances where it is necessary to have a maximum yield of the momomer, it may be necessary to take such precautions that the alkali used in promoting oxyethylation of glycerol, be removed before subsequent reaction. This, of course, can be done in any simple manner by conversion to sodium chloride, sodium sulfate,- or any suitable procedure.

In the preceding examples of the Completed monomeric derivative, Examples 1 to 10, inclusive,

no reference is made to the elimination of such alkaline catalyst, in view of the effectiveness of the low multiple polymers as demulsifiers. Previous reference has been made to the fact that the carboxylic hydrogen atom might be variously replaced by substituents including organic radicals, for instance, the radicals obtained from alcohols, hydroxylated amines, non-hydroxylated amines, polyhydric alcohols, etc. Obviously the reference is also true, in that a free hydroxyl group may be esterified with a selected acid, varying from such materials as ricinoleic acid to oleic acid, including alcohol acids, such as hydroxy acetic acid, lactic acid, ricinoleic acid and also polybasic acids of the kind herein contemplated.

With the above facts in mind, it becomes obvious that what has been previously said as to polymerization, with the suggestion that by-products or cogenerie materials were formed, may be recapitulated with greater definiteness, and one can readily apreciate that the formation of heatrearranged derivatives or compounds must take place to a greater or lesser degree. Thus, the products herein contemplated may be characterized by being monomers of the type previously described, or esterification polymers, or the heatrearranged derivatives of the same, and thus including the heat-rearranged derivatives of both the polymers and esterification monomers, separately and jointly. Although the class of materials speciflcally contemplated in this instance is a comparatively small and narrow class of a broad genus, yet it is obviously impossible to present any adequate formula which would contemplate the present series in their complete ramification, except in a manner employed in the hereto appended claims.

Although the products herein contemplated vary so broadly in their characteristics, i. e., monomers through sub-resinous polymers, soluble products, water-emulsifiable oils or compounds,

hydrotropic materials, balsams, sub-resinous materials, semi-resinous materials, and the like, yet there is always present the characteristic unitary hydrophile structure related back to the oxyalkylation, particularly the oxyethylation of the glycerol used as the raw material. When our new product is used as a demulsifier in the resolution of oil field emulsions, the demulsifier may be added to the emulsion at the ratio of 1 part in 10,000, 1 part in 20,000, 1 part in 30,000, or for that matter, 1 part in 40,000. In such ratios it well may be that one cannot differentiate between the solubility of a compound completely soluble in water in any ratio, and a semi-resinous product apparently insoluble in water in ratios by which ordinary insoluble materials are characterized. However, at such ratios the importance must reside in interfacial position and the ability to usurp, preempt, or replace the interfacial position previously accupied perhaps by the emulsifying colloid. In any event, reviewed in this light, the obvious common property running through the entire series, notwithstanding variation in molecular size and physical make-up, is absolutely apparent. Such statement is an obvious oversimplification of the rationale underlying demulsification, and does not even consider the resistance of an interfacial film to crumbling, displacement, being forced into solution, altered wetability, and the like. As to amidification polymers, for instance, where Z is a polyaminoamide radical, seewhat is said subsequently.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGENERS Example 1 COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGENERS Example 2 The same procedure is followed as in the preceding example, except that polymerization is continued, using either a somewhat longer reaction time, or it may be, a somewhat higher temperature, or both, so as to obtain a material having a molecular weight of approximately three to four times that of the initial product.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGENERS Example 3 The same procedure is followed as in Examples 1 and 2, preceding, except that one employs as reactants amides derived from tris(hydroxymethyl) aminomethane, instead of amides of diethanolamine.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED CocENERs Ewample 4 The same procedure is followed as in Examples 1 to 3, preceding, except that one polymerizes a mixture instead of a single monomer, for instance, a mixture of materials of the kind described in Completed monomeric derivative, Ex-

. ample 3, andinC'ompleted monomeric derivative,

It is understood, of course, that the polymer 1 ized product need not be obtained as a result of a two-step procedure. In other words, one need not convert the reactants into the monomer and then subsequently convert the monomer into the polymer. through the monomer to the polymer in one step. Indeed, the formation of the monOmer and polymerization may take place simultaneously. This is especially true ifpolymerization is conducted in the absence of an inert solvent, as previously described, and if one uses a. comparatively higher temperature, for instance, approximately 220 C. for polymerization. Thus, one pound mole of oxyethylated glycerol maleate of the kind described, ratio 1 to 15, up to 1 toZl, is mixed with two moles of hydroxyethyl ricinoleoamide and reacted for. 30 hours at approximatel 220 C., until the mass is homogeneous. It is stirred constantly during reaction. Polyfunctionality may reside in dehydration (etherization) groups attached to dissimilar molecules.

The fact that the polymerized and heat-rearranged products can be made in a single step, illustrates a phenomenon which Sometimes occurs either in such instances Where alcoholic bodies of the kind herein illustrated are contemplated as reactants, or where somewhat kindred alcoholic bodies are employed. The reactants may be mixed mechanically to give a homogeneous mixture, or if the reactants do not mix to give a homogeneous mixture, then early in the reaction stage there is formed, to a greater or lesser degree, suificient monomeric materials so that a homogeneous system is present. Subsequently, as reaction continues, the system may become heterogeneous and exist in two distinct phases, one being possibly an oily body of moderate viscosity, and the other being a heavier material, which is sticky or sub-resinous in nature. In many instances it will be found that the thinner liquid The reactants may be converted of two hydroxyl Iii material is a monomer and the more viscou or resinous material is a polymer, as previously described. Such product can be used for demulsification by adding a solvent which will mutually dissolve the two materials, or else, by separating the two heterogeneous phases and employing each as if it were a separate product of reaction.

Materials of the kind herein contemplated may find uses as wetting, detergent, and leveling agents in the laundry, textile, and dyeing industry; as wetting agents and detergents in the acid washing of fruit, in the acid Washing or buiding stone and brick; as a wetting agent and spreader in the application of asphalt in road building and the like, as a constituent of soldering flux preparations; as a flotation reagent in the flotation separation of various minerals; for flocculation and coagulation of various aqueous suspensions containing negatively charged particles such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifiers for cosmetics, spray oils, water-repellent textile finish, etc. These uses are by no means exhaustive.

However, the most important phase of the present invention, as far as industrial application goes, is concerned with the use of the materials previously described as demulsifiers for water-inoil emulsions, and more specifically, emulsions of Water or brine in crude petroleum.

We have found that the particular chemical compounds or reagents herein described may also be used for other purposes, for instance, as a break inducer in doctor treatment of the kind intended to. sweeten gasoline. (See U. S. Patent No. 2,157,223, dated May 9, 1939, to Sutton.)

Chemical compounds of "the kind herein described are also of value as surface tension depressants in the acidization of calcareous oilbearing strata by means of strong mineral acid, such as hydrochloric acid. Similarly, some members are efiective as surface tension depressants or wetting agents in'the flooding of exhausted oilbearing strata.

As to using compounds of the kind herein described as fiooding agents for recovering oil from subterranean strata, reference is made to the pro cedure described in detail in U. S. Patent No. 2,- 226,119, dated December 24, 1949, to De Groote and Keiser. As to using compounds of the kind herein described as demulsifiers, or in particular as surface tension depressants in combination with mineral acid or aoidization of oil-bearing strata, reference is made to U. S. Patent No. 2,233,- 383, dated February 25, 1941, to De Groote and Keiser.

cognizance must be taken of the fact that the surface of the reacting vessel may increase or decrease reaction rate and degree of polymerization, for instance, an iron reaction vessel speeds up reaction and polymerization, compared with a glass-lined vessel.

As has been previously indicated, th sub-genus employed as an alcohol in the present instance is one of a series of alcoholic compounds which are contemplated in our co-pending application Serial Nos. 497,118, 497,119, 497,120, 497,121, 497,122, 497,124, 497,125, 497,126, 497,127, 497,128, 497,129, 497,130, 497,131, 497,132, 497,133, 497,134, and

497,135, filed August 2, 1943.

Having thus described our invention, What we claim as new and desire to secure by Letters Patent is:

l. A member of the class consisting of sub-resinous ester-linked acyl derivatives of a water-insoluble detergent-forming monocarboxy acid amide of the formula:

in which R200 is the acyl radical of the aforementionedmonocarboxy acid and having at least 8 and not over 32 carbon atoms, and R3 is a member of the class consisting of alkanol radicals, and alkylene-oxyalkanol radicals; B4 is a hydrocarbon radical having not over 6 carbon atoms; 112 represents a numeral Varying from 0 to 1, n represents a numeral varying from 1 to 2, and q represents a numeral varying from 0 to 1 with the proviso that m and n, plus q, must equal 2; the acyl group substituted for a reactive oxygemlinked hydrogen atom of said hydroxylated amide being the acyl radical of an acidic fractional ester of the formula:

in which OCR1CO is the acyl radical of a polycarboxy acid having not over 8 carbon atoms; 2 represents a metallic cation; RO is a member of the class consisting of ethylene oxide radicals, propylene oxide radicals, butylene oxide radicals, and glycid radicals, and n represents a numeral varying from 3 to 10, and n" represents a numeral varying from to 2, and n represents a numeral varying from 1 to 3, with the proviso that the sum of 11., plus 11", equals 3.

2. The ester of claim 1, wherein m in both occurrences is zero.

3. The ester of claim 1, wherein m in both occurrences is zero, and RzCO is the acyl radical of a higher fatty acid having 18 carbon atoms.

4. The ester of claim 1, wherein m in both occurrences is zero and RzCO is the acyl radical of an unsaturated higher fatty acid having 18 carbon atoms.

5. The ester of claim 1, wherein m in both occurrences is zero and RzCO is the acyl radical of an unsaturated higher fatty acid having 18 carbon atoms, and R is an ethylene radical.

6. The ester of claim 1, wherein m in both occurr-ances is zero, R2CO is the acyl radical of an unsaturated higher fatty acid having 18 carbon atoms, R is an ethylene radical, and the polycarboxy acid is dicarboxy.

7. The ester of claim 1, wherein m in both occurrences is zero, R2CO is the acyl radica1 of an unsaturated higher fatty acid having 18 carbon atoms, R is an ethylene radical, and --OCR1CO is a maleic acid radical.

8. The ester of claim 1, wherein m in both occurrences is zero, RzCO is the acyl radical of an unsaturated higher fatty acid having 18 carbon atoms, R is an ethylene radical, and -OCR1CO is a phthalic acid radical.

9. The ester of claim 1, wherein m in both occurrences is zero, RzCO is the acyl radical of an unsaturated higher fatty acid having 18 carbon atoms, R is an ethylene radical, and -OCR1CO- is an adipic radical.

10. The method of manufacturing esters, described in claim 1, which consists in reacting a water-insoluble detergent-forming monocarboxy acid amide of the formula:

R20 ON-[Rl1n in which RC0 is the acyl radical of the aforementioned monocarboxy acid, and R3 is a member of the class consisting of alkanol radicals and alkyleneoxyalkan-ol radicals; R4 is a hydrocarbon radical having not over six carbon atoms; m represents a numeral varying from 0 to 2, n represents a numeral varying from 1 to 2, and q represents a numeral varying from 0 to 1, with the proviso that m and n, plus q, must equal 2; with an acidic ester of the formula:

[(RO),. OOCR1COOZ]n" CzHsOs [(RO),.'OOCR1COOH]..M

in which -OCR1CO-- is the acyl radical of a polycarboxy acid having not over 8 carbon atoms; Z represents a metallic cation; Rr-O is a member of the class consisting of ethylene oxide radicals, propylene oxide radicals, butylene oxide radicals and. glycid radicals, and n represents a numeral varying from 3 to 10, and n" represents a numeral varying from 0 to 2, and n represents a numeral varying from 1 to 3, with the proviso that the sum of n"+n"= 3.

MELVIN DE GROOTE. BERNHARD KEISER. 

